Classifications

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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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  • C08K5/5399—Phosphorus bound to nitrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/07—Flat, e.g. panels
  • B29C48/08—Flat, e.g. panels flexible, e.g. films
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  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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  • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
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• • C—CHEMISTRY; METALLURGY
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/02—Synthetic macromolecular particles
  • B32B2264/0214—Particles made of materials belonging to B32B27/00
  • B32B2264/0228—Vinyl resin particles, e.g. polyvinyl acetate, polyvinyl alcohol polymers or ethylene-vinyl acetate copolymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/306—Resistant to heat
  • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2307/00—Properties of the layers or laminate
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2457/04—Insulators
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
  • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/02—Flame or fire retardant/resistant

Definitions

• the present invention relates to a flame-retardant polycarbonate resin composition. Specifically, the present invention relates to a polycarbonate resin composition having excellent sheet/film moldability and flame retardance, a sheet or film obtained by using the same, and a method for the production thereof.
• Polycarbonate resins have many excellent characteristics such as excellent heat resistance, mechanical properties and electric properties and high dimensional accuracy, and therefore are widely used in a variety of fields.
• molded products obtained by injection molding, extrusion molding or the like of polycarbonate resins are utilized for automotive materials, materials for electrical and electronic equipments, housing materials, materials for the production of parts in other industrial fields, etc.
• flame retarded polycarbonate resin compositions are used as members for information/mobile devices such as computers, notebook computers, tablet terminals, smartphones and mobile phones, office automation equipments such as printers and copying machines, etc.
• Patent Documents 1 and 2 describe a flame-retardant polycarbonate resin composition, wherein a phosphazene compound or a condensed phosphoric acid ester-based compound is used as a flame retardant.
• this is a composition optimized mainly for injection molding, and the viscosity of the resin component is low.
• a polyfluoroethylene having fibril-forming ability which has large shrinkage at the time of molding and poor dispersibility, is blended in the composition, it is unsuitable for the production of a film or sheet.
• the film/sheet has a large thickness unevenness, and when a test piece having a thickness of 0.25 mm or less is subjected to the UL-94 VTM burning test, it is evaluated as non-conforming because tearing of the film during flame contact exceeds the bench mark.
• Patent Document 3 describes a resin sheet, wherein a polycarbonate, a phosphorus-based flame retardant and a polyfluoroethylene are blended.
• the document does not describe any viscosity (flow value) of the resin composition.
• a product of a polycarbonate having high flowability, but also a phosphorus-based flame retardant that increases flowability and a fibrillated polyfluoroethylene having poor dispersibility are blended in the composition of the Examples, and for this reason, a film/sheet obtained by the melt extrusion method has a large thickness unevenness.
• UL-94 VTM burning test it is evaluated as non-conforming because tearing of the film during flame contact exceeds the bench mark.
• Patent Document 1 Japanese Laid-Open Patent Publication No. 2013-224349
• Patent Document 2 Japanese Laid-Open Patent Publication No. 2011-057888
• Patent Document 3 Japanese Laid-Open Patent Publication No. 2005-200588
• the problems to be solved by the present invention are to provide a polycarbonate resin composition, which is suitable for the production of a film/sheet having excellent thin-wall flame retardance with a small thickness unevenness, and a sheet/film obtained by using the same.
• the present inventors diligently made researches in order to solve the above-described problems, and found that when using a resin composition consisting of a mixture containing a polycarbonate, a flame retardant and a fluoropolymer having a specific flow value, a resin film/sheet having excellent flame retardance with a small thickness unevenness can be provided.
• a resin composition consisting of a mixture containing a polycarbonate, a flame retardant and a fluoropolymer having a specific flow value
• a resin film/sheet having excellent flame retardance with a small thickness unevenness can be provided.
• the present invention is as described below.
• a polycarbonate resin composition which contains 73 to 94.5% by mass of a polycarbonate resin (A), 5 to 25% by mass of a phosphorus-based flame retardant (B) and 0.1 to 2% by mass of a fluoropolymer (C), the composition having a flow value of 1 ⁇ 0.01 to 10 ⁇ 0.01 cm 3 /sec at 280° C.
• the phosphorus-based flame retardant (B) is a phosphazene compound or a condensed-type phosphoric acid ester.
• the sheet or film according to item [6] which has a thickness of 10 to 1000 ⁇ m.
• a method for producing a sheet or film which comprises extrusion molding the polycarbonate resin composition according to any one of items [1] to [5].
• a film/sheet having excellent flame retardance with a small thickness unevenness is provided.
• Such a film/sheet can be suitably used as an insulation film for electrical and electronic equipments, a film for nameplates and a film for cases such as battery packs.
• the type of the polycarbonate resin (A) (hereinafter sometimes referred to as “the component (A)”) to be used in the present invention is not particularly limited, but an aromatic polycarbonate resin is particularly preferably used in terms of heat resistance and flame retardance.
• the polycarbonate resin is a branched or unbranched thermoplastic polymer or copolymer, which is obtained by reacting a dihydroxy compound or this and a small amount of a branching agent with phosgene or triphosgene or carbonic acid diester.
• the method for producing the polycarbonate resin is not particularly limited, and it is possible to use a polycarbonate resin produced by a conventionally known phosgene method (interfacial polymerization method), melting method (transesterification method) or the like. Further, in the case of using the melting method, it is possible to use a polycarbonate resin in which the amount of OH groups of terminal groups is adjusted.
• the ratio of the polycarbonate resin (A) in the polycarbonate resin composition of the present invention (100% by mass) is 73 to 94.5% by mass, and in terms of heat resistance, it is preferably 80 to 94.5% by mass, and more preferably 85 to 93% by mass.
• dihydroxy compound as a raw material examples include 2,2-bis(4-hydroxyphenyl)propane (i.e., “bisphenol A”), tetramethylbisphenol A, bis(4-hydroxyphenyl)-p-diisopropylbenzene, hydroquinone, resorcinol and 4,4-dihydroxydiphenyl. Two or more of these compounds may be used in combination. In terms of heat resistance and availability, it is preferred to use bisphenol A as the main component.
• the polycarbonate resin containing bisphenol A as the main component is a polycarbonate resin, wherein the ratio of bisphenol A in bisphenols used is 60 to 100 mol %, and preferably 90 to 100 mol %. Further, it is also possible to use a compound in which at least one tetraalkylphosphonium sulfonate is bound to the above-described aromatic dihydroxy compound.
• the polycarbonate resin may be a copolymer mainly composed of a polycarbonate resin such as a copolymer of the dihydroxy compound and a compound having a siloxane structure.
• a part of the above-described dihydroxy compound may be substituted with a branching agent.
• the branching agent is not particularly limited, and examples thereof include a polyhydroxy compound such as phloroglucin, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptene-2, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 2,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptene-3, 1,3,5-tri(4-hydroxyphenyl)benzene and 1,1,1-tri(4-hydroxyphenyl)ethane, and 3,3-bis(4-hydroxyaryl)oxyindole (i.e., “isatinbisphenol”), 5-chloroisatin, 5,7-dichloroisatin and 5-bromoisatin.
• the amount of the compound to be used for substitution is usually 0.01 to 10 mol %, and
• polycarbonate resin (A) As the polycarbonate resin (A), among the above-described ones, preferred is a polycarbonate resin derived from 2,2-bis(4-hydroxyphenyl)propane (i.e., “bisphenol A”) or a polycarbonate copolymer derived from 2,2-bis(4-hydroxyphenyl)propane (i.e., “bisphenol A”) and another aromatic dihydroxy compound.
• bisphenol A 2,2-bis(4-hydroxyphenyl)propane
• bisphenol A a polycarbonate copolymer derived from 2,2-bis(4-hydroxyphenyl)propane
• polycarbonate resins may be used solely, or two or more of them may be used by mixing thereof.
• a monovalent hydroxy compound for example, an aromatic hydroxy compound may be used.
• the monovalent aromatic hydroxy compound include m- and p-methylphenol, m- and p-propylphenol, p-tert-butylphenol and p-long chain alkyl substituted phenol.
• the polycarbonate resin (A) is a polycarbonate resin having a viscosity-average molecular weight [Mv] of 12,000 or more.
• a carbonate resin having a viscosity-average molecular weight of less than 12,000 is referred to as “carbonate oligomer” and distinguished from the polycarbonate resin (A).
• the molecular weight of the polycarbonate resin (A) to be used in the present invention may be arbitrarily determined according to intended use and may be suitably selected and determined mainly depending on the blending ratio of the phosphorus-based flame retardant (B) and the fluoropolymer (C). From the viewpoint of moldability, strength of molded products, etc., regarding the molecular weight of the aromatic polycarbonate resin (A), the viscosity-average molecular weight [Mv] thereof is preferably 28,000 to 50,000, and more preferably 35,000 to 40,000. The molecular weight of the aromatic polycarbonate resin (A) is controlled by the amount of the terminating agent to be used, polymerization time, etc.
• the viscosity-average molecular weight is 30,000 or more, dispersibility of the fluoropolymer (C) in the polycarbonate resin (A) is further improved, shrinkage of a film during molding derived from the fluoropolymer is sufficiently suppressed, and a film/sheet with a small thickness unevenness can be obtained.
• the viscosity-average molecular weight is 50,000 or less, reduction in the flowability of the polycarbonate resin composition of the present invention can be suppressed, and problems such as reduction in the extrusion processability due to increase of screw torque, reduction in the production rate and deterioration of additives due to increase of resin temperature can be suppressed.
• the viscosity-average molecular weight [Mv] of the polycarbonate resin or carbonate oligomer can be measured by the below-described method.
• the value of the limiting viscosity [ ⁇ ] is obtained by carrying out the measurement of the specific viscosity [ ⁇ sp ] with each solution concentration [C] (g/dl) and calculation according to the below-described formula.
• the polycarbonate resin composition of the present invention may contain a carbonate oligomer in addition to the polycarbonate resin (A).
• the carbonate oligomer may affect flowability and heat resistance of the resin composition.
• the content of the carbonate oligomer which is a low-molecular-weight component, is preferably as small as possible.
• the amount of the carbonate oligomer is large and/or the average molecular weight of the carbonate-based resin is small, for example, dispersibility of the fluoropolymer (C) may be reduced; and shrinkage of the fluoropolymer may occur during molding because the viscosity of the resin composition is low.
• the blending amount of the carbonate oligomer is preferably 0 to 3 parts by weight, more preferably 0 to 1 parts by weight, and even more preferably substantially 0 part by weight relative to the total weight (100 parts by weight) of the polycarbonate resin (A). That is, it is preferred that the carbonate oligomer is substantially not contained.
• the viscosity-average molecular weight of the carbonate-based resin component consisting of the polycarbonate resin (A) and the carbonate oligomer is preferably 28,000 to 50,000, and more preferably 35,000 to 40,000.
• the molecular weight distribution (Mw/Mn) of the carbonate-based resin component consisting of the polycarbonate resin (A) and the carbonate oligomer is preferably 2.0 to 3.0, more preferably 2.4 to 2.8, and particularly preferably 2.4 to 2.7 from the viewpoint of flowability and heat resistance.
• the polycarbonate resin composition of the present invention contains the phosphorus-based flame retardant (B) for the improvement of flame retardance.
• the ratio of the phosphorus-based flame retardant (B) in the polycarbonate resin composition (100% by mass) is 5 to 25% by mass. When the ratio is 5% by mass or more, sufficient flame retardance can be imparted thereby. When the ratio is 25% by mass or less, reduction in heat resistance of the resin composition can be suppressed.
• the ratio is preferably 6 to 20% by mass, and more preferably 7 to 15% by mass.
• phosphorus-based flame retardant (B) a phosphoric acid ester-based flame retardant, a phosphazene-based flame retardant, etc. can be used.
• phosphorus-based flame retardant (B) such flame retardants may be used solely, or two or more of them may be used as a mixture.
• a phosphoric acid ester-based flame retardant is preferably used because it has high flame retardant effect and also has flowability improvement effect.
• the phosphoric acid ester-based flame retardant is not limited, but it is particularly preferably a phosphoric acid ester-based compound represented by general formula (IIa) below.
• R 1 , R 2 , R 3 and R 4 each independently represent a C 1-8 alkyl group which may be substituted with a C 1-8 alkoxy group, or a C 6-20 aryl group which may be substituted with a C 1-8 alkyl group or phenyl which may be substituted with a C 1-8 alkyl group; p, q, r and s are each independently 0 or 1; t is an integer of 0 to 5; and X represents an arylene group or a divalent group represented by formula (Hip) below.)
• B is a single bond, —C(CH 3 ) 2 —, —SO 2 —, —S— or —O—.
• examples of the aryl group of R 1 to R 4 include a phenyl group and a naphthyl group.
• examples of the arylene group of X include a phenylene group and a naphtylene group.
• the compound represented by general formula (IIa) is a phosphoric acid ester, and when t is larger than 0, the compound is a condensed phosphoric acid ester (including a mixture).
• the condensed phosphoric acid ester is particularly preferably used.
• phosphoric acid ester-based flame retardant represented by general formula (IIa) above include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresylphenyl phosphate, octyldiphenyl phosphate, diisopropylphenyl phosphate, bisphenol A tetraphenyl diphosphate, bisphenol A tetracresyl diphosphate, bisphenol A tetraxylyl diphosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetracresyl diphosphate, hydroquinone tetraxylyl diphosphate, resorcinol tetraphenyl diphosphate, resorcinol bisdixylenyl phosphate,
• triphenyl phosphate preferred are triphenyl phosphate, bisphenol A tetraphenyl diphosphate, resorcinol tetraphenyl diphosphate, resorcinol bisdi-2,6-xylenyl phosphate, etc.
• Examples of commercially-available phosphoric acid ester-based flame retardants include FP-600 manufactured by ADEKA Corporation and PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.
• phosphoric acid ester-based flame retardants may be used solely, or two or more of them may be used as a mixture.
• the phosphazene-based flame retardant can suppress reduction in heat resistance of the resin composition due to addition of the flame retardant more than the phosphoric acid ester-based flame retardant, and therefore can be used as an effective phosphorus-based flame retardant.
• the phosphazene-based flame retardant is an organic compound having a —P ⁇ N— bond in the molecule.
• Preferred examples of the phosphazene-based flame retardant include a cyclic phosphazene compound represented by general formula (IIIa) below, a linear phosphazene compound represented by general formula (IIIb) below, and a crosslinked phosphazene compound in which at least one phosphazene compound selected from the group consisting of compounds of general formulae (IIIa) and (IIIb) below is crosslinked with a crosslinking group.
• the crosslinked phosphazene compound those obtained by crosslinking with a crosslinking group represented by general formula (IIIc) below are preferred in terms of flame retardance.
• m is an integer of 3 to 25; and R 5 s may be the same or different and represent an aryl group or an alkylaryl group.
• n is an integer of 3 to 10,000; Z represents a —N ⁇ P(OR 5 ) 3 group or a —N ⁇ P(O)OR 5 group; and Y represents a —P(OR 5 ) 4 group or a —P(O)(OR 5 ) 2 group.
• R 5 s may be the same or different and represent an aryl group or an alkylaryl group.
• cyclic and/or linear phosphazene compounds represented by general formulae (IIIa) and (IIIb) include those in which R 5 is a C 6-20 aryl group which may be substituted with a C 1-6 alkyl group.
• More specific examples thereof include: a cyclic and/or linear C 1-6 alkyl C 6-20 aryloxy phosphazene such as phenoxyphosphazene, (poly)tolyloxyphosphazene (e.g., o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, o,m-tolyloxyphosphazene, o,p-tolyloxyphosphazene, m,p-tolyloxyphosphazene, o,m,p-tolyloxyphosphazene, etc.) and (poly)xylyloxyphosphazene; and a cyclic and/or linear C 6-20 aryl C 1-10 alkyl C 6-20 aryloxy phosphazene such as (poly)phenoxytolyloxyphosphazene (e.g., phenoxy-o-tolyloxyphos
• a cyclic and/or linear phenoxyphosphazene a cyclic and/or linear C 1-3 alkyl C 6-20 aryloxy phosphazene, and a C 6-20 aryloxy C 1-3 alkyl C 6-20 aryloxy phosphazene (e.g., a cyclic and/or linear tolyloxyphosphazene, a cyclic and/or linear phenoxytolylphenoxyphosphazene, etc.).
• C 1-6 means that “the carbon number is 1 to 6”, and the same applies to “C 6-20 ”, “C 1-10 ”, etc.
• (poly)phenoxy . . . ” means one or both of “phenoxy . . . ” and “polyphenoxy . . . ”.
• cyclic phosphazene compound represented by general formula (IIIa) a cyclic phenoxyphosphazene in which R 5 is a phenyl group is particularly preferred.
• the cyclic phenoxyphosphazene compound is preferably a compound represented by general formula (IIIa), wherein m is an integer of 3 to 8, and may also be a mixture of compounds in which the numbers for m differ from each other.
• Specific examples thereof include compounds such as hexaphenoxycyclotriphosphazene (compound in which m is 3), octaphenoxycyclotetraphosphazene (compound in which m is 4) and decaphenoxycyclopentaphosphazene (compound in which m is 5), and mixtures thereof.
• preferred is a mixture containing 50% by mass or more of a compound in which m is 3, 10 to 40% by mass of a compound in which m is 4 and 30% by mass or less of compounds in which m is 5 or more.
• ammonium chloride is reacted with phosphorus pentachloride at 120 to 130° C. to obtain a mixture of cyclic and linear chlorophosphazenes, from which cyclic chlorophosphazenes such as hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene and decachlorocyclopentaphosphazene are taken out, and then these are subjected to substitution with a phenoxy group, thereby obtaining the above-described cyclic phenoxyphosphazene compound.
• cyclic chlorophosphazenes such as hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene and decachlorocyclopentaphosphazene are taken out, and then these are subjected to substitution with a phenoxy group, thereby obtaining the above-described cyclic phenoxyphosphazene compound.
• linear phosphazene compound represented by general formula (IIIb) a linear phenoxyphosphazene in which R 5 is a phenyl group is particularly preferred.
• linear phenoxyphosphazene compound examples include compounds obtained by subjecting a chloride of the cyclic phenoxyphosphazene compound obtained by the above-described method (e.g., hexachlorocyclotriphosphazene) to ring-opening polymerization at 220 to 250° C. and substituting a linear dichlorophosphazene having a polymerization degree of 3 to 10,000 obtained with a phenoxy group.
• n in general formula (IIIb) is preferably 3 to 1,000, more preferably 3 to 100, and even more preferably 3 to 25.
• Examples of the crosslinked phenoxyphosphazene compound include compounds having a crosslinked structure of a 4,4′-diphenylene group such as a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue), a compound having a crosslinked structure of a 2,2-(4,4′-diphenylene)isopropylidene group, a compound having a crosslinked structure of a 4,4′-oxydiphenylene group, and a compound having a crosslinked structure of a 4,4′-thiodiphenylene group.
• a 4,4′-diphenylene group such as a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue), a compound having a crosslinked structure of a 2,2-(4,4′-diphenylene)isopropylidene group, a compound having a crosslinked structure of a 4,4′-oxydiphenylene group, and a compound having
• crosslinked phosphazene compound a crosslinked phenoxyphosphazene compound, wherein a cyclic phenoxyphosphazene compound in which R 5 in general formula (IIIa) is a phenyl group is crosslinked with a crosslinking group represented by general formula (IIIc) above, or a crosslinked phenoxyphosphazene compound, wherein a linear phenoxyphosphazene compound in which R 5 in general formula (IIIb) above is a phenyl group is crosslinked with a crosslinking group represented by general formula (IIIc) above, is preferred in terms of flame retardance, and a crosslinked phenoxyphosphazene compound, wherein the cyclic phenoxyphosphazene compound is crosslinked with a crosslinking group represented by general formula (IIIc) above, is more preferred.
• the content of the phenylene group in the crosslinked phenoxyphosphazene compound is usually 50 to 99.9%, and preferably 70 to 90% based on the total number of the phenyl group and the phenylene group in the cyclic phosphazene compound represented by general formula (IIIa) and/or the linear phenoxyphosphazene compound represented by general formula (IIIb).
• the crosslinked phenoxyphosphazene compound is particularly preferably a compound not having a free hydroxyl group in the molecule.
• the phosphazene-based flame retardant is preferably at least one selected from the group consisting of a cyclic phenoxyphosphazene compound represented by general formula (IIIa) above and a crosslinked phenoxyphosphazene compound, wherein a cyclic phenoxyphosphazene compound represented by general formula (IIIa) above is crosslinked with a crosslinking group.
• phosphazene-based flame retardants include “Rabitle FP-110” and “Rabitle FP-110T” manufactured by Fushimi Pharmaceutical Co., Ltd. and “SPS100” manufactured by Otsuka Chemical Co., Ltd. which are cyclic phenoxyphosphazenes.
• phosphazene-based flame retardants may be used solely, or two or more of them may be used as a mixture.
• the fluoropolymer (C) is added in order to prevent dripping of a burning material of the polycarbonate resin composition of the present invention.
• the fluoropolymer examples include a fluoroolefin resin.
• the fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure.
• the polymer or copolymer containing a fluoroethylene structure is a polymer mainly composed of a fluoroethylene structure (structural unit).
• the ratio of the fluoroethylene structure (structural unit of fluoroethylene) is preferably 40 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 60 to 100% by mass of all the monomer units constituting the fluoropolymer.
• the number-average molecular weight of polytetrafluoroethylene is not particularly limited, but it is preferably 3,000,000 to tens of millions (e.g., 3,000,000 to 90,000,000).
• a polydifluoroethylene resin examples thereof include a polydifluoroethylene resin, a polytetrafluoroethylene resin, a tetrafluoroethylene/hexafluoropropylene copolymer resin and a tetrafluoroethylene/perfluoroalkylvinylether copolymer resin.
• a polytetrafluoroethylene resin in terms of flame retardance.
• a fluoroethylene resin having fibril-forming ability is also preferably used.
• “fibril-forming ability” means that resins show tendency to be bound together to become fibrous due to an external action such as a shear force.
• fluoroethylene resin having fibril-forming ability examples include “Teflon (registered trademark) 6J” and “Teflon (registered trademark) 640J” manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd. and Polyflon F-series (e.g., “Polyflon F201L”, “Polyflon F103”, “Polyflon FA500B” and “Polyflon FA500H”) manufactured by Daikin Industries, Ltd.
• Teflon (registered trademark) 6J” and “Teflon (registered trademark) 640J” manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.
• Polyflon F-series e.g., “Polyflon F201L”, “Polyflon F103”, “Polyflon FA500B” and “Polyflon FA500H” manufactured by Daikin Industries, Ltd.
• examples of commercially-available aqueous dispersions of the fluoroethylene resin having fibril-forming ability include “Teflon (registered trademark) 30J” and “Teflon (registered trademark) 31-JR” manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd. and “Fluon D-1” manufactured by Daikin Industries, Ltd.
• the form of the fluoropolymer (C) is not particularly limited, but it is preferably in the form of fine particles.
• a fluoroethylene polymer having a multilayer structure wherein a fluoroethylene polymer is coated with a polymer obtained by polymerizing a vinyl-based monomer (vinyl-based polymer) (modified polytetrafluoroethylene).
• modified polyfluoroethylene is advantageous in terms of handling at the time of compounding of raw materials.
• the modified polyfluoroethylene include a polystyrene-fluoroethylene complex, a polystyrene-acrylonitrile-fluoroethylene complex, a polymethyl methacrylate-fluoroethylene complex and a polybutyl methacrylate-fluoroethylene complex.
• acrylic-modified polyfluoroethylene having a multilayer structure consisting of a (meth)acrylic resin (e.g., polymethyl methacrylate and polybutyl methacrylate) and a fluoroethylene resin.
• the fluoropolymer (C) is in the form of uncoated particles (i.e., non-core-shell type uniform particles) made of a polymer or copolymer containing a tetrafluoroethylene structure or particles obtained by coating the polymer or copolymer with the above-described vinyl-based polymer.
• one type of a fluoropolymer may be contained, or two or more types of fluoropolymers may be contained with any combination and any ratio.
• the ratio of the fluoropolymer in the polycarbonate resin composition of the present invention (100% by mass) is 0.1 to 2% by mass.
• the ratio of the fluoropolymer is less than 0.1% by mass, the effect of improving flame retardance exerted by the fluoropolymer may be insufficient.
• the ratio of the fluoropolymer is more than 2% by mass, poor outer appearance, thickness unevenness and reduction in mechanical strength of a molded product obtained by molding the polycarbonate resin composition may be caused.
• the ratio of the fluoropolymer is more preferably 0.5 to 1% by mass.
• the aromatic polycarbonate resin composition of the present invention may contain resin components other than the polycarbonate resin (A) and the fluoropolymer (C) within a range in which the purpose of the present invention is not impaired.
• resin components which can be blended include a polystyrene resin, a high impact polystyrene resin, a hydrogenated polystyrene resin, a polyacrylstyrene resin, an ABS resin, an AS resin, an AES resin, an ASA resin, an SMA resin, a polyalkyl methacrylate resin, a polymethacrylic methacrylate resin, a polyphenylether resin, a polycarbonate resin other than the component (A), an amorphous polyalkylene terephthalate resin, a polyester resin, an amorphous polyamide resin, poly-4-methylpentene-1, a cyclic polyolefin resin, an amorphous polyarylate resin and polyethersulfone.
• the aromatic polycarbonate resin composition of the present invention may further contain various additives within a range in which the effects of the present invention are not reduced.
• additives include a stabilizer, an antioxidant, a mold release agent, an ultraviolet absorber, a stain pigment, an antistatic agent, a flame retardant, an impact strength modifier, a plasticizer, a dispersing agent, an antimicrobial agent and an inorganic filler (a silicate compound, glass fiber, carbon fiber, etc.).
• One type of such an additive for resin may be contained, or two or more types of such additives may be contained with any combination and any ratio.
• the method for producing the polycarbonate resin composition of the present invention is not limited, and a wide range of publicly-known methods for producing a polycarbonate resin composition can be employed.
• Specific examples thereof include a method in which the polycarbonate resin (A), the phosphorus-based flame retardant (B) and the fluoropolymer (C) of the present invention, and other components, which are blended according to need, are mixed together in advance using, for example, a mixing machine such as a tumbler, a Henschel mixer and a super mixer, and then the mixture is melt-kneaded using a mixing machine such as a Bunbury mixer, a roller, a Brabender, a single screw kneading extruder, a twin screw kneading extruder and a kneader.
• a mixing machine such as a tumbler, a Henschel mixer and a super mixer
• a mixing machine such as a Bunbury mixer, a roller, a Brabender, a single screw kneading extruder, a twin screw kneading extruder and a kneader.
• the polycarbonate resin composition of the present invention is characterized in that the flow value of the resin composition at 280° C. is 1 ⁇ 0.01 to 10 ⁇ 0.01 cm 3 /sec.
• the flow value (Q value) as used herein refers to a value measured by the method described in JIS K7210-1: 2014 Annex JA.
• a flow tester CFD500D manufactured by Shimadzu Corporation is used, a die having a hole diameter of 1.0 mm and a length of 10 mm is used, and the amount of molten resin discharged at a test temperature of 280° C. with a test force of 160 kg/cm 2 and a preheating time of 420 sec is used as the flow value ( ⁇ 0.01 cm 3 /sec).
• the flow value of the resin composition is preferably 2 ⁇ 0.01 cm 3 /sec or more. Further, in terms of further reduction of thickness unevenness of the sheet/film, the flow value of the resin composition is preferably 9 ⁇ 0.01 cm 3 /sec or less, and more preferably 8 ⁇ 0.01 cm 3 /sec or less.
• the flow value within the above-described range is suitable for the production of films/sheets by means of extrusion molding.
• the present inventors focused attention on the flow value of the resin composition, and found that the flow value is associated with thickness unevenness and thin-wall flame retardance in the case of thin layers.
• thickness unevenness of a thin-layer product can be suppressed and flame retardance can be imparted to the product.
• a resin composition having a flow value of 10 ⁇ 0.01 to 50 ⁇ 0.01 cm 3 /sec is generally used, and the range of the flow value differs from the range of the present invention.
• the flow value of “Iupilon (registered trademark) H-4000” manufactured by Mitsubishi Engineering-Plastics Corporation, which is used for injection molding is within the above-described range (10 ⁇ 0.01 to 50 ⁇ 0.01 cm 3 /sec).
• the flow value of the polycarbonate resin composition can be adjusted within a desired range by controlling the blending ratio of the constituents (A) to (C), the type of each of the constituents (A) to (C) or the like.
• the flow value can be adjusted within a desired range by controlling the below-described items.
• the polycarbonate resin composition of the present invention can be made into molded bodies with various forms.
• the polycarbonate resin composition of the present invention it is possible to provide a thin-walled molded article having excellent flame retardance, which is difficult to be realized by conventional polycarbonate resin compositions.
• Examples of applications of the molded article of the present invention include electrical and electronic equipments, office automation equipments, information terminal devices, machine components, home appliances, vehicle components, building components, various containers, leisure goods/sundries and components for lighting equipments, etc.
• the molded article of the present invention is suitably used for electrical and electronic equipments, office automation equipments, information terminal devices, home appliances, components for lighting equipments, etc.
• the polycarbonate resin composition of the present invention is suitably used for molding into a sheet or film, and a sheet or film having excellent thin-wall flame retardance with a small thickness unevenness is obtained.
• the method for producing a sheet or film from the polycarbonate resin composition of the present invention is not particularly limited.
• molding methods such as the melt extrusion molding method, the solution casting method, the blow molding method and the inflation molding method can be used.
• the extrusion molding method from the viewpoint of continuous productivity.
• the method for producing a sheet or film includes a step of extrusion molding the polycarbonate resin composition.
• a non-reinforced thermoplastic resin layer may be laminated on one or both of surfaces of the outer layer of the sheet or film made of the polycarbonate resin.
• a laminated sheet or film, which has a thermoplastic resin layer on at least one surface of the polycarbonate resin layer, is provided.
• thermoplastic resin to be laminated may contain various additives.
• additives include a stabilizer, an antioxidant, a mold release agent, an ultraviolet absorber, a stain pigment, an antistatic agent, a flame retardant, an impact strength modifier, a plasticizer, a dispersing agent and an antimicrobial agent.
• One type of such an additive for resin may be contained, or two or more types of such additives may be contained with any combination and any ratio.
• the “sheet” generally refers to a thin and flat product whose thickness is small considering the length and width thereof
• the “film” refers to a thin and flat product whose thickness is extremely small considering the length and width thereof, wherein the maximum thickness is arbitrarily limited, which is usually supplied in the form of a roll.
• the “sheet” is not clearly distinguished from the “film”, and these terms are used as the same meaning.
• the thickness of the film or sheet obtained from the polycarbonate resin composition of the present invention is preferably 10 to 1000 ⁇ m, more preferably 30 to 500 ⁇ m, and even more preferably 30 to 200 ⁇ m.
• the film or sheet obtained from the polycarbonate resin composition of the present invention has a small thickness unevenness.
• the flow value (Q value) of the resin composition pellet was evaluated by reference to the method described in JIS K7210-1: 2014 Annex JA.
• a flow tester CFD500D manufactured by Shimadzu Corporation was used, a die having a hole diameter of 1.0 mm and a length of 10 mm was used, and the amount of molten resin discharged at a test temperature of 280° C. with a test force of 160 kg/cm 2 and a preheating time of 420 sec was used as the flow value ( ⁇ 0.01 cm 3 /sec). Note that the evaluation is described as “flow value” in the tables.
• the film thickness distribution of the resin film was measured using a contact type desk-top off-line thickness measurement device (TOF-5R) manufactured by Yamabun Electronics Co., Ltd.
• the thickness of the central portion of the film was measured at 140 points in total at 10 mm intervals along the flow direction (MD direction) at the time of extrusion molding, and the average value and the standard deviation of the film thickness were obtained to evaluate variation of the film thickness. Note that the evaluation is described as “average film thickness” and “film thickness standard deviation” in the tables.
• the case where the film thickness standard deviation is 0 ⁇ m or more and less than 2 ⁇ m can be judged as “very good”, the case where it is 2 ⁇ m or more and less than 4 ⁇ m can be judged as “good”, and the case where it is 4 ⁇ m or more can be judged as “poor”.
• the flame retardance of the polycarbonate resin film was evaluated by a method according to the UL94/VTM burning test established by Underwriters Laboratories (UL, US) using a cut film (width: 50 mm ⁇ length: 200 mm ⁇ thickness: 50 ⁇ m).
• UL94/VTM burning test established by Underwriters Laboratories (UL, US) using a cut film (width: 50 mm ⁇ length: 200 mm ⁇ thickness: 50 ⁇ m).
• Measurement samples were cut into the above-described size (width: 50 mm ⁇ length: 200 mm ⁇ thickness: 50 ⁇ m).
• Sample A A sample left at 23° C. and 50% RH for 48 hours was referred to as Sample A, and a sample left at 70° C. for 168 hours and then cooled at 23° C. and at 20% RH or lower for 4 hours was referred to as Sample B. For each of them, one set consisting of 5 samples was prepared.
• a line was drawn on each sample at a position 125 mm away from the short side thereof in the direction parallel to the short side, and the sample was wound around a stick having a diameter of 12.7 mm in a manner such that the short side was in the vertical direction.
• the portion 75 mm or more above the 125 mm mark was fixed with a pressure sensitive tape and then the stick was pulled out.
• the upper end of the sample was closed in order to prevent the stack effect during the test.
• each sample was set vertically, and an absorbent cotton was placed 300 mm below the sample.
• a Bunsen burner having a diameter of 9.5 mm and a length of flame of 20 mm as a heating source was placed in a manner such that the tube of the burner was positioned 10 mm below the lower end of the sample.
• the burning time (t1) after the flame was moved away for the first time was compared to the burning time (t2) after the flame was moved away for the second time, and the longer one (t1 or t2) was evaluated as “Maximum burning time of each sample”.
• the total burning time of 5 samples (the total of t1+t2 of 5 samples) was evaluated as “Total burning time of 5 samples”.
• the presence or absence of a burning falling object which causes absorbent cotton ignition was evaluated as the presence or absence of “cotton ignition due to dripping”.
• a polycarbonate resin composition having a composition described in Tables 2 and 3 was obtained as described below.
• components were kneaded at a screw rotation speed of 200 rpm, at a discharge rate of 20 kg/hour, and at a barrel temperature of 300° C., and the molten resin extruded into a strand-like shape was rapidly cooled in a water bath and pelletized using a pelletizer.
• the flow value of the obtained pellet is shown in Tables 2 and 3.
• a film was obtained from the obtained pellet made of the polycarbonate resin composition by means of extrusion molding as described below.
• the polycarbonate resin compositions of the Examples contain 73 to 94.5% by mass of the polycarbonate resin (A), 5 to 25% by mass of the phosphorus-based flame retardant (B) and 0.1 to 2% by mass of the fluoropolymer (C), wherein the flow value at 280° C. is adjusted to 1 ⁇ 0.01 to 10 ⁇ 0.01 cm 3 /sec. All the films produced from these polycarbonate resin compositions of the Examples had excellent flame retardance with a small thickness unevenness.
• a film/sheet having excellent thin-wall flame retardance with a small thickness unevenness can be produced by using a polycarbonate resin composition, which contains the polycarbonate resin (A), the phosphorus-based flame retardant (B) and the fluoropolymer (C) within predetermined ranges respectively, and which has a specific flow value.

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